Portable visual assay of Bacillus anthracis biomarker based on ligand-functionalized dual-emission lanthanide metal-organic frameworks and smartphone-integrated mini-device.

A single-functionalized ligand single-Ln based dual-emission Ln-MOF fluorescent sensor was established for portable and visual dipicolinic acid (DPA, Bacillus anthracis biomarker) detection. First, a theory calculation-based prediction model was developed for designing single-functionalized ligand single-Ln dual-emission Ln-MOFs. The model consisted of three calculation modules: intramolecular hydrogen bonds, excited state energy levels, and coordination stability with Ln of ligands. Tb and Eu were selected as metal luminescence centers, PTA-X (PTA: p-phthalic acid, X = NH, CH, H, OH) with different functional groups as one-step functionalization ligands, and the luminescent feature of four Tb-MOFs and four Eu-MOFs was predicted with the model. Coupled with prediction results and experimental verification results, Tb-PTA-OH was rapidly determined to be the sole dual-emission Ln-MOF. Then, Tb-PTA-OH was applied to DPA detection by ratiometric fluorescence, and an ultra-low limit of detection (13.4 nM) was obtained, which is much lower than the lowest anthrax infectious dose (60 μM). A portable visual assay method based on paper-microchip and smartphone integrated mini-device was further established (limit of qualification 0.48 μM). A new sensing mechanism and a "triple gates" selectivity mechanism to DPA were proposed. This work reveals guidelines for material design and mini-device customization in detecting hazardous substances.